WO2021032834A1 - Composition solide de détergent - Google Patents

Composition solide de détergent Download PDF

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Publication number
WO2021032834A1
WO2021032834A1 PCT/EP2020/073326 EP2020073326W WO2021032834A1 WO 2021032834 A1 WO2021032834 A1 WO 2021032834A1 EP 2020073326 W EP2020073326 W EP 2020073326W WO 2021032834 A1 WO2021032834 A1 WO 2021032834A1
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WO
WIPO (PCT)
Prior art keywords
acid
solid
crystalline
solid composition
amount
Prior art date
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PCT/EP2020/073326
Other languages
English (en)
Inventor
Hélène Julie Marie ARLABOSSE
Liam Edward DAVIES
Alexandre François BOUX DE CASSON
Robert Jan MOLL
Original Assignee
Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Ip Holdings B.V., Unilever Global Ip Limited, Conopco, Inc., D/B/A Unilever filed Critical Unilever Ip Holdings B.V.
Priority to EP20758223.0A priority Critical patent/EP4017957B1/fr
Priority to CN202080058501.9A priority patent/CN114286854A/zh
Priority to ES20758223T priority patent/ES2944450T3/es
Publication of WO2021032834A1 publication Critical patent/WO2021032834A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the present invention relates to a solid composition comprising aminopolycarboxylate, organic acid, bismuth/zinc and water.
  • the invention further relates to a process for the manufacture of the solid composition.
  • Detergent products typically contain several different active components, including builders, surfactants, enzymes and bleaching agents.
  • Surfactants are employed to remove stains and soil and to disperse the released components into the cleaning liquid.
  • Enzymes help to remove stubborn stains of proteins, starch and lipids by hydrolyzing these components.
  • Bleach is used to remove stains by oxidizing the components that make up these stains.
  • 'builders' complexing agents
  • Phosphorus- containing builder components are generally considered to be "high- performance" builders.
  • the use of phosphorous based builders in detergent products has however led to environmental problems such as eutrophication.
  • Examples of such alternative builders are based on aminopolycarboxylates.
  • a drawback of many of such aminopolycarboxylates is that they tend to be hygroscopic.
  • WO 2014/086662 discloses a solid glutamic acid N,N-diacetic acid (GLDA) comprising a combination of GLDA, sulphuric acid and sodium sulfate crystals. Also described is a process of producing a solid GLDA composition comprising the consecutive steps of:
  • class corrosion inhibitors which preferably is (semi-)transparent/(semi-)translucent, which is suitable for use in detergent products, preferably further having improved dissolution/dispersion properties.
  • a solid composition comprising: a) from 25 to 88 wt. % free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) from 10 to 60 wt. % free acid equivalent of non-crystalline organic acid different from aminopolycarboxylate; and c) from 0.0005 to 4 wt. % of non-crystalline bismuth, non-crystalline zinc or a combination thereof; and d) from 0.7 to 25 wt. % of water, wherein the organic acid has an average molecular mass of at most 500 Dalton, the molecular mass being based on the free acid equivalent.
  • the solid composition of the invention comprises non-crystalline chiral polycarboxylate, non-crystalline organic acid, and non-crystalline bismuth and/or non-crystalline zinc as may be measured by WAXS using the method set-out in the Examples. Having little or no crystals, the solid composition is highly light transmitting. Of course, as desired further ingredients can be mixed into the solid composition to provide a desired level of light transmittance (e.g. provide semi-translucency/semi-transparency). As such the solid composition of the invention has a tunable light transmittance, as well as tunable light scattering, which is highly desirable in the making of detergent products. Surprisingly such a solid composition could be made using only known detergent actives. The composition also has low hygroscopicity (e.g. as compared to aminopolycarboxylate solids as such), which improves (storage) stability.
  • hygroscopicity e.g. as compared to aminopolycarboxylate solids as such
  • a further benefit which was observed is that the use of non-crystalline zinc and/or bismuth can provide an appreciable visual metallic sheen to the solid. Even more surprisingly it was found that use of bismuth greatly improves the gloss of the solid composition.
  • the organic acid is homogenously mixed with the chiral aminopolycarboxylate and the bismuth/zinc and molecularly interacts with it (although not being covalently bound to it). This is believed to prevent these components from (substantially) crystallizing and to form a glass-like matrix.
  • the composition can be free of further added crystal formation inhibitors
  • the solid according to the invention can surprisingly be made with the following process, which relates to the second aspect of the invention:
  • Process for the manufacture of the solid according to the invention comprising the consecutive steps of: I. providing an aqueous solution comprising: a) free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) free acid equivalent of non-crystalline organic acid different from a); and c) non-crystalline bismuth, non-crystalline zinc or a combination thereof, wherein the weight ratio of a):b) is from 1:2 to 8.8:1; and
  • the desiccated liquid that is formed by reducing the water content of the solution to 25 wt. % or less is in a viscous (or rubbery) state.
  • the viscosity increases to a level where the material becomes solid.
  • a hard(er) solid can be obtained.
  • This process offers the advantage that it allows for the production of the solid composition in the form of (shaped) pieces.
  • the process can be used to coat a solid substrate with the solid composition by coating the substrate with the hot liquid desiccated mixture and allowing the hot mixture to cool down when in contact with the substrate. It was found that the solid composition of the present invention has thermoplastic behaviour which can suitably be used in the preparation of a detergent product and which also makes it more suitable for extrusion.
  • the solid can be used to make a detergent product having added visual appeal.
  • it can form a detergent product by itself or be used as part of a detergent product comprising (visually distinct) further parts.
  • such detergent products with enhanced visual appeal can be made while only using (further) detergent actives.
  • a further aspect of the invention is the use of the solid composition according to the invention to provide a detergent product which in part or in whole is translucent, preferably in part or in whole is translucent and more preferably further has a metallic sheen.
  • a further aspect of the invention is the use of the solid composition according the invention to provide a detergent product which in part or in whole has an improved gloss.
  • Weight percentage is based on the total weight of the solid or the detergent product as indicated, unless otherwise stated. It will be appreciated that the total weight amount of ingredients will not exceed 100 wt. %. Amounts expressed in wt. % parts can exceed a total of 100%. Whenever an amount or concentration of a component is quantified herein, unless indicated otherwise, the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients. It is furthermore to be understood that the verb "to comprise” and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
  • indefinite article “a” or “an” does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements.
  • the indefinite article “a” or “an” thus usually means “at least one”. Unless otherwise specified all measurements are taken at standard conditions. Whenever a parameter, such as a concentration or a ratio, is said to be less than a certain upper limit it should be understood that in the absence of a specified lower limit the lower limit for said parameter is 0.
  • solid according to its commonplace usage.
  • a wineglass is considered a solid in common place usage although in a strict physical sense it is an extremely viscous liquid.
  • the solid is not in the form of a (fine) powder.
  • aminopolycarboxylate includes its partial or full acids unless otherwise specified.
  • the salts, rather than the acids, of the aminopolycarboxylates are more preferred, and particularly preferred are the alkali salts thereof.
  • organic acid includes partial or full alkali salts thereof unless otherwise specified.
  • Concentrations expressed in ‘free acid equivalent’ refer to the concentration of an aminopolycarboxylate or an acid assuming that the aminopolycarboxylate of acid is exclusively present in fully protonated from.
  • the following table shows how the free acid equivalent concentrations can be calculated for some (anhydrous) aminopolycarboxylates and (anhydrous) acid salts.
  • the term ‘translucency’ is used as meaning the ability of light in the visible spectrum to pass through the solid at least in part. To quantify, preferably it is evaluated based on a path-length of 0.5 cm through the solid, measuring the amount of light passing through.
  • the solid is deemed to be translucent if under the aforementioned measurement conditions within the wavelength range of 400 to 700 nm it has a maximum Transmittance of at least 5%.
  • the solid is deemed to be transparent if within the aforementioned wavelength range it has a maximum Transmittance of at least 20%.
  • the Transmittance is defined as the ratio between the light intensity measured after the light has passed through the sample of solid and the light intensity measured when the sample has been removed.
  • the solid composition is capable of parallel Light transmittance, meaning the transmitting of Light without appreciable Light scattering.
  • the degree of Light scattering is less than 40%, 30%, 20%, 10%, 5%, 3%, 1%.
  • “Scattering” as used herein preferably refers to both wide angle scattering and small angle scattering. Wide angle scattering causes what is referred to as haze or loss of contrast, whereas small/narrow angle scattering reduces the see-through quality or clarity. Hence it is preferable that haze is minimized and clarity maximized by minimal narrow and wide angle scattering.
  • the total Light transmittance, wide angle scattering and small angle scattering can be measured using a Haze-Gard I - Transparency Meter (SHBG4775), and according to Supplier instructions. Gloss was measured as explained in the Examples.
  • Aminopolycarboxylates (chiral or non-chiral) are well known in the detergent industry and sometimes referred to as aminocarboxylate chelants. They are generally appreciated as being strong builders. Chirality is a geometric property of molecules induced by the molecules having at least one chiral centre. A chiral molecule is non- superimposable on its mirror image.
  • the chiral aminopolycarboxylate as used in the invention can comprise all its molecular mirror images. Chiral and preferred aminopolycarboxylates are glutamic acid N,N-diacetic acid
  • GLDA methylglycinediacetic acid
  • EDDS ethylenediaminedisuccinic acid
  • IDS iminodisuccinic acid
  • I DM iminodimalic acid
  • GLDA methylglycinediacetic acid
  • EDDS ethylenediaminedisuccinic acid
  • IDS iminodisuccinic acid
  • I DM iminodimalic acid
  • GLDA methylglycinediacetic acid
  • EDDS ethylenediaminedisuccinic acid
  • IDS iminodisuccinic acid
  • I DM iminodimalic acid
  • GLDA methylglycinediacetic acid
  • EDDS ethylenediaminedisuccinic acid
  • IDS iminodisuccinic acid
  • I DM iminodimalic acid
  • GLDA methylglycinediacetic acid
  • EDDS ethylenediaminedisucc
  • non-chiral aminopolycarboxylates are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid-N,N-diacetic acid (ASDA) , hydroxyethylene-diaminetetraacetic acid (HEDTA), hydroxyethylethylene- diaminetriacetic acid (HEEDTA) , iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleic acid and (EDDMAL),
  • the solid of the invention comprises from 25 to 88 wt. % free acid equivalent of chiral aminopolycarboxylates.
  • a particularly preferred amount of chiral aminopolycarboxylate is from 30 to 70 wt. % and more preferably from 35 to 60 wt. %.
  • the weight of the chiral aminopolycarboxylates is measured as based on the free acid equivalent.
  • the solid of the invention contains at least 50 wt. %, more preferably at least 75 wt. % free acid equivalent of GLDA, MGDA, EDDS, IDS, I DM or a mixture thereof, based on the total weight of free acid equivalent of chiral aminopolycarboxylate. More preferably, the solid contains at least 50 wt. %, more preferably at least 75 wt. % free acid equivalent of GLDA, MGDA, EDDS or mixtures thereof, based on the total weight of free acid equivalent of chiral aminopolycarboxylate.
  • the free acid equivalent of aminopolycarboxylate essentially consists of free acid equivalent of GLDA, MGDA, EDDS or a mixture thereof.
  • GLDA in general is most appreciated as it can be made from bio-based materials (e.g. monosodium glutamate, which itself can be made as by-product from corn fermentation). Also GLDA is highly biodegradable.
  • the solid according to the invention comprises organic acid, said acid not being an aminopolycarboxylate.
  • the organic acid used in the solid according to the invention can otherwise be any organic acid. Particularly good results were achieved with organic acids being polyacids (i.e. acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids.
  • the organic acids used in the invention have an average molecular mass of at most 500 Dalton preferably of at most 400 Dalton and more preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent.
  • the organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.
  • the organic acids preferably are those which are also found naturally occurring, such as in plants.
  • organic acids of note are acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, their salts, or mixtures thereof.
  • Citric acid, lactic acid, acetic acid and aspartic acid are even more preferred.
  • Citric acid and/or its salt are especially beneficial as, besides acting as builder are also highly biodegradable.
  • the solid contains at least 10, more preferably at least 15, even more preferably at least 20, most preferably at least 25 wt. wt. % free acid equivalent of citric acid.
  • the solid of the invention comprises from 10 to 60 wt. % of the organic acid, the weight being based on the equivalent free acid. Preferred is a total amount of organic acid of from 15 to 55 wt. %, more preferably of from 25 to 50 wt. %, based on the weight of the free acid equivalents.
  • the weight ratio of a):b) is from 1:2 to 1:0.15, preferably from 1:1.5 to 1:0.4, more preferably from 1:1.4 to 1: 0.5, based on the weight of the free acid equivalents.
  • the solid composition comprises a total amount of non-crystalline bismuth, non crystalline zinc or a combination thereof of from 0.0005 to 4 wt. %. Surprisingly these can be incorporated into the solid composition, which comprises in large part of aminopolycarboxylate and organic acid, while not crystallizing. This is the more surprising given the amount of free water in the solid can be very low with most of the water bound to the aminopolycarboxylate. It was further found that incorporating non-crystalline zinc and especially bismuth provides a metallic sheen to the solid which forms an important consumer que to highlight glass corrosion prevention effects.
  • the solid composition of the invention is translucent or transparent and has a metallic sheen.
  • the metallic sheen can be of any colour but preferably is green, blue or grey and preferably is grey.
  • An advantageous amount of non-crystalline bismuth is from 0.001 to 3.5 wt. %, more preferably from 0.005 to 3.0 wt. %, even more preferably from 0.01 to 2.5 wt. % and still even more preferably from 0.05 to 1.0 wt. %.
  • An advantageous amount of non crystalline zinc is from 0.001 to 3.5 wt. %, more preferably from 0.005 to 3.0 wt. %, even more preferably from 0.01 to 2.5 wt. % and still even more preferably from 0.05 to 1.0 wt. %.
  • the advantageous total amount of non-crystalline zinc and non-crystalline bismuth is from 0.001 to 3.5 wt.
  • the bismuth and zinc are preferably added as a salt.
  • bismuth is added as bismuth citrate and zinc as zinc sulphate. It will be appreciated that only part of the total weight of the bismuth citrate stems from the bismuth and as such when adding bismuth citrate as a source of bismuth the amount should be appropriate to get the desired wt.
  • the molecular weight of bismuth citrate is 780.65 g/mol. It has the formula C12H8B1K5O14 which has one bismuth atom. The weight of the bismuth is 208.98 g/mol. Hence to add 1 wt. % of bismuth one needs to add 3.7 wt. % of bismuth citrate.
  • the solid according to the invention comprises from 0.7 to 25 wt. % of water. It was surprisingly found that use of such a water content provided a solid with a good balance of hardness and plasticity. Depending on the water level the solid can be a harder solid with water levels in the lower range of from 0.7 to 25 wt. %.
  • the general plasticity and thermoplastic properties offer the significant practical advantage that the solid can be (machine) worked with a low chance of breakage or of forming cracks. Also, not unimportantly, it can provide an improved sensory experience when handled by the consumer.
  • the lower-ends and upper-ends can be readily combined, such as an amount of water of from preferably 1.0 to 20 wt. %, more preferably of from 1.4 to 15 wt. % even more preferably of from 1.5 to 8 wt. %.
  • the latter ranges provide a further optimum between suitable hardness, reduced brittleness especially when including sulfonated polymer and/or polycarboxylate polymer (as described below).
  • the water-activity a w of the solid according to the invention can be 0.7 or lower. Preferred is a water-activity a w of at most 0.6, and further preferred of at most 0.5. The preferred lower limit of water activity a w may be 0.15.
  • the total amount of non-crystalline chiral aminopolycarboxylate, non- crystalline organic acid, non-crystalline bismuth, non-crystalline zinc and water is from 60 to 100 wt. % based on the total weight of the solid according to the invention, preferably from 70 to 100 wt. %, more preferably from 80 to 100 wt. %, even more preferably from 90 to 100 wt. % and still even more preferably from 95 to 100 wt. % of the total weight of the solid according to the invention.
  • Such highly preferred solid composition comprises: a) from 30 to 70 wt. % free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) from 15 to 55 wt. % free acid equivalent of non-crystalline organic acid different from aminopolycarboxylate; and c) from 0.001 to 3.5 wt. % of non-crystalline bismuth, non-crystalline zinc or a combination thereof d) from 0.7 to 15 wt. % of water; wherein a), b), c) and d) form from 70 to 100 wt. % of the total weight of the solid composition.
  • solid composition comprises: a) from 35 to 60 wt. % free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) from 25 to 50 wt. % free acid equivalent of non-crystalline organic acid different from aminopolycarboxylate; and c) from 0.005 to 3.0 wt. % of non-crystalline bismuth, non-crystalline zinc or a combination thereof d) from 1.0 to 10 wt. % of water; wherein a), b), c) and d) form from 80 to 100 wt. % of the total weight of the solid composition.
  • solid composition according to the invention comprises: a) from 35 to 60 wt. % free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) from 25 to 50 wt. % free acid equivalent of non-crystalline organic acid different from aminopolycarboxylate; and c) from 0.01 to 1.0 wt. % of non-crystalline bismuth, non-crystalline zinc or a combination thereof d) from 2.0 to 8 wt. % of water; wherein a), b), c) and d) form from 90 to 100 wt. % of the total weight of the solid composition. pH profile
  • the solid of the invention preferably has the following pH profile: the pH of a solution of the solid made by dissolving the solid in water in a 1 : 1 weight ratio is at most 10.0, as measured at 25 degrees Celsius.
  • a pH profile improves stability of the solid. Particularly good results were achieved for said pH profile being at most 9.0, more preferably at most 8.0.
  • Many detergents products are overall alkaline.
  • the pH of a solution made by dissolving 1 wt. % of the solid in water is at least 5.0 and more preferably at least 6.0 and more preferably at least 6.5 as measured at 25 degrees Celsius.
  • the solid of the invention may comprise further ingredients, such as further detergent active components.
  • the solid of the invention preferably comprises sulfonated polymer, polycarboxylate polymer or a combination thereof in a total amount of from 0.3 to 50 wt. %, more preferably from 5 to 40 wt. %, even more preferably from 10 to 35 wt. % and still even more preferably from 15 to 25 wt. %, as based on the free acid equivalent of the polymer.
  • the improved plasticity is beneficial as it makes the solids easier to (mechanically) work (i.e. at raised temperatures) and makes it easier to manufacture detergent product comprising the solid.
  • a higher glass transition temperature is beneficial as it aids stability of the solid during storage and handling, in particular in view of temperature stresses. That being said a glass transition temperature which is not too high will aid quick dissolution of the product in warm water as it helps to liquefy the solid during use by increasing surface area.
  • the glass transition temperature (T g ) of the solid is less than 80 degrees Celsius, more preferably from 10 to 60 degrees Celsius, even more preferably from 15 to 50 degrees Celsius and most preferably from 20 to 40 degrees Celsius.
  • the reduction in hygroscopicity was more pronounced if the polymer (in particular the carboxylate polymer) used has a lower average molecular weight maximum.
  • the sulfonated polymer that is employed in accordance with the present invention can be a copolymer or a homopolymer.
  • the sulfonated polymer is a copolymer.
  • Suitable sulfonated polymers preferably have a mass averaged molecular mass of 3,000 to 50,000, more preferably from 4,500 to 35,000.
  • the solid composition comprises sulfonated polymer comprising polymerized units of one or more unsaturated sulfonate monomers selected from 2-acrylamido methyl-1 -propanesulfonic acid, 2-methacrylicamido-2-methyl-1- propanesulphonic acid, 3-methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid.
  • the solid composition comprises sulfonated polymer comprising polymerized units of one or more unsaturated sulfonate monomers represented by the following formula:
  • R ⁇ R 2 , R 3 , R 4 independently represent C1-C6 alkyl or hydrogen
  • X represents hydrogen or alkali.
  • the sulfonated polymer is a copolymer comprising polymerized units of monoethylenically unsaturated C3-C6 monocarboxylic acid. More preferably, the sulfonated copolymer comprises the following monomers in polymerised form:
  • the monoethylenically unsaturated C3-C6 monocarboxylic acid in the sulfonated copolymer are selected from acrylic acid, meth(acrylic) acid and combinations thereof.
  • sulfonated copolymers having the following combined properties:
  • polycarboxylate polymer here is used to also cover the acid form and is different from the acid that is present in the solid.
  • Suitable polycarboxylate polymers have an average molar mass Mw of from 500 to 500.000. They may be modified or unmodified, but preferably are unmodified. Also they can be co-polymers or homopolymers, although homopolymers are considered more beneficial.
  • Polycarboxylate polymers having an average molar mass (Mw) of from 900 to 100.000, more preferably 1100 to 10.000 gave better results in terms of further improving the benefits described of adding polymer.
  • the solid comprises polycarboxylate polymer selected from polyacrylate, copolymers of polyacrylate, polymaleate, copolymers of polymaleate, polymethacrylate, copolymers of polymethacrylate, polymethyl-methacrylate, copolymers of polymethyl methacrylate, polyaspartate, copolymers of polyaspartate, polylactate, copolymers of polylactate, polyitaconates, copolymers of polyitaconates and combinations thereof.
  • polycarboxylate polymer selected from polyacrylate, copolymers of polyacrylate, polymaleate, copolymers of polymaleate, polymethacrylate, copolymers of polymethacrylate, polymethyl-methacrylate, copolymers of polymethyl methacrylate, polyaspartate, copolymers of polyaspartate, polylactate, copolymers of polylactate, polyitaconates, copolymers of polyitaconates and combinations thereof.
  • Highly preferred polycarboxylate polymers are polyacrylates.
  • Suitable polyacrylates are commercially available, such as from BASF under the tradename Sokalan PA 13 PN, Solakan PA 15, Sokalan PA 20 PN, Sokalan PA 20, Sokalan PA 25 PN, Sokalan PA 30, Sokalan 30 CL, Sokalan PA 40, Sokalan PA 50, Sokalan PA 70 PN, Sokalan PA 80 S and Sokalan PA 110 S.
  • polyacrylates having the following combined properties:
  • polycarboxylate polymers • which are homopolymers.
  • polycarboxylate polymers • which are homopolymers.
  • polycarboxylate polymers are the more preferred.
  • the solid of the invention may, depending on the aminopolycarboxylate and acid used, be colored and for example have a yellowish tinge.
  • the translucency of such solid can be further improved by adding an opposing colorant of the color wheel, which is preferably a dye.
  • an opposing colorant of the color wheel which is preferably a dye.
  • yellow opposes blue on the color wheel, and violet opposes green This will render the solid in essence to be more colorless, which can be preferred.
  • typical dyes need be added in relatively small amounts to be effective. Hence their level is suggested not to be above 0.5 wt. % and preferably is at most 0.2 wt. %.
  • the solid composition preferably contains not more than 30 wt. % of ingredients other than aminopolycarboxylate, zinc, bismuth, organic acid, polyacrylate, colorants and water, more preferably no more than 20 wt. %, still even more preferably no more than 10 wt. %, still even more preferably no more than 5 wt. %, still even more preferably no more than 2 wt. % and still even more preferably essentially no further ingredients are present. If further ingredients are present in the solid composition these are preferably water-soluble non-crystalline ingredients.
  • the solid composition of the invention can have any suitable shape and size.
  • the solid composition may be in any form but is not a (fine) powder. The latter is since, when in a (fine) powder, the improved translucency and gloss of the solid composition will be difficult to appreciate due to the inherent light scattering properties of (fine) powders).
  • it is preferably present in at least one continuous volume of from 0.2 to 15 cm 3 , even more preferably from 0.4 to 10 cm 3 , most preferably from 0.5 to 5 cm 3 . Said preferred volumes allows the solid of the invention to be easily visible to the naked eye, allowing it to be better appreciated for its visual appeal.
  • the solid may be present in any suitable shape.
  • a detergent product When used, as part of a detergent product or otherwise, it is preferably has at least one continuous, preferably overall flat, surface area of 0.5 to 25 cm 2 , even more preferably from 1.0 to 10 cm 2 , most preferably from 1.5 to 5 cm 2 . Said preferred sizes allows it to be better appreciated for its visual appeal by the untrained human eye.
  • the solid preferably has a maximum Transmittance within the wavelength range of 400 to 700 nm of at least 5%, more preferably of at least 10%, even more preferably of at least 20%, yet more preferably of at least 25% and most preferably of least 30%.
  • the solid has an average Transmittance in the wavelength range of 400 to 700 nm of at least 5%, more preferably of at least 10%, even more preferably of at least 20% and most preferably of at least 25%.
  • the solid composition may form a detergent product by itself or form part of a detergent product.
  • the detergent product comprises the solid according to the first aspect of the invention in an amount of from 1 to 90 wt. %, preferably in an amount of from 2 to 85 wt. %, more preferably of from 5 to 70 wt. %.
  • the particularly preferred amount of the solid of the invention is from 5 to 60 wt. %, more preferably 10 to 50 wt. % and even more preferably 15 to 40 wt. %.
  • the particularly preferred amount of the solid of the invention is from 10 to 85 wt. %, more preferably 20 to 80 wt. % and even more preferably 40 to 70 wt. %.
  • the particularly preferred amount of the solid of the invention is from 1 to 60, more preferably 2 to 50 wt. %, and even more preferably,
  • the solid is visually distinct from the remainder of the detergent product part(s).
  • the visual distinctiveness of the solid of the invention is preferably based on the solid having (a higher) translucency compared to the other detergent product solid part(s).
  • the distinctiveness of the solid can be further enhanced by a suitable distinctive colouring. This can be by making it of more intense or of less intense colour (e.g. colourless).
  • colourants such as dyes and/or pigments are effective in low amounts and as such this is typically not problematic.
  • the solid of the invention is used to provide a detergent product with enhanced visual appeal.
  • the solid can be present in any suitable shape or shapes, such as in one or more layers, lines (e.g. rods, beams), spherical or cuboid shapes or combinations thereof.
  • Preferred shapes are the following: cuboid, cylinder, sphere, bar, X-bar, pyramid, prism, cone, dome and (circular) tube. Of these more preferred shapes are bar, X-bar, cylinder, cuboid, (circular) tube and sphere.
  • the solid of the invention in the detergent product may act as a matrix and hold part, or the whole, of the further ingredients in the detergent product.
  • the solid of the invention may be used to form a (partial) skin.
  • the solid acts as a translucent matrix holding one or more distinct bodies, which can be visible in the matrix.
  • the bodies being preferably in the shape of spheres or cubes.
  • the bodies being preferably coloured.
  • the skilled person is endowed with the capability to use the solid of the invention to his advantage when making more appealing detergent products.
  • ways of using the solid in a detergent product in which the solid remains distinctly visible can be appreciated for it translucent and/or glossy nature are highly preferred.
  • the detergent product according to the invention comprises the solid according to the invention.
  • the detergent product (as a whole) will comprise chiral aminopolycarboxylate, organic acid, zinc and/or bismuth, and water by virtue of this.
  • the detergent product in addition preferably comprises, but preferably in the other part(s) than that of the solid of the invention, at least one further detergent active, and preferably one or more of enzymes, enzyme stabilizers, bleaching agents, bleach activator, bleach catalyst, bleach scavengers, drying aids, silicates, metal care agents, colorants, perfumes, lime soap dispersants, anti-foam, anti-tarnish, anti-corrosion agents, surfactants and further builders.
  • Further builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetraacetic acid.
  • Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
  • the detergent product comprises sodium carbonate in the range from 5 to 50 wt%, most preferably 10 to 35 wt%.
  • Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g.
  • zeolite A zeolite A
  • zeolite B also known as zeolite P
  • zeolite C zeolite C
  • zeolite X zeolite Y
  • zeolite P-type as described in EP-A-0,384,070.
  • the detergent product may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions. Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred further builders.
  • the builder may be crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15wt. %.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M2O. AI2O3. 0.8-6 S1O2, where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • the ratio of surfactants to alumuminosilicate is preferably greater than 5:2, more preferably greater than 3:1.
  • phosphate builders may be used.
  • the term ’phosphate’ embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • the detergent product is a non-phosphate built detergent product, i.e., contains less than 1 wt% of phosphate and preferably essentially no phosphate.
  • the detergent product according to the invention comprises at most 5 wt. %, more preferably at most 1 wt. % and particularly essentially no phosphorous based builders.
  • phosphorous based builders are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP), ethylenediaminetetra- methylenephosphonate (EDTMP), tripolyphosphate, pyrophosphate.
  • Alkali carbonate is appreciated in view of its double-function as builder and buffer and is preferably present in the detergent product. If present the preferred amount of alkali carbonate in the detergent product is from 2 to 75 wt.%, more preferably from 3 to 50 wt.% and even more preferably from 5 to 20 wt.%. Such level of alkali carbonate provides good Ca 2+ and Mg 2+ ion scavenging for most types of water hardness levels, as well as other builder effects, such as providing good buffering capacity.
  • the preferred alkali carbonates are sodium- and/or potassium carbonate of which sodium carbonate is particularly preferred.
  • the alkali carbonate present in the detergent product of the invention can be present as such or as part of a more complex ingredient (e.g. sodium carbonate in sodium percarbonate).
  • the detergent product of the invention comprises 0.5 to 70 wt. % of surfactant, more preferably 2 to 50 wt. %.
  • the surfactant can be non-ionic or anionic.
  • the particularly preferred amount of surfactant is from 0.5 to 25 wt.%, preferably 2 to 15 wt. %. In case of toilet bowl rim detergent products the particularly preferred amount of surfactant is from 0.5 to 55, preferably 10 to 40 wt. %. In case of laundry detergent products the particular preferred amount of surfactant is from 2 to 70, preferably 10 to 35 wt. %.
  • nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents” Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon’s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • the surfactants used are saturated.
  • Suitable non-ionic surfactants which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Preferably low-foaming nonionic surfactants are used particularly from the group of alkoxylated alcohols.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms for example from coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 mol of EO per mol of alcohol are preferred.
  • the preferred ethoxylated alcohols include for example C12-14 alcohols with 3 EO to 4 EO, C9-12 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-19 alcohol with 5 EO.
  • Preferred tallow fatty alcohols with more than 12 EO have from 60 to 100 EO, and more preferably from 70 to 90 EO.
  • Particularly preferred tallow fatty alcohols with more than 12 EO are tallow fatty alcohols with 80 EO.
  • Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are likewise particularly preferentially used.
  • nonionic surfactants originate from the groups comprising alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/ polyoxyethylene/ polyoxypropylene (PO/EO/P ).
  • structurally complex surfactants such as polyoxypropylene/ polyoxyethylene/ polyoxypropylene (PO/EO/P ).
  • PO/EO/PO polyoxypropylene/ polyoxyethylene/ polyoxypropylene
  • the most preferred nonionic surfactants are according to the formula: wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein n is from 0 to 3 and m is from 15 to 40, and even more preferably wherein n is 0 and m is from 18 to 25.
  • Surfactants according to this formula were particularly useful in reducing spotting of dishware treated in a machine dish washer.
  • Such nonionic surfactants are commercially available, e.g. under the tradename Dehypon WET (Supplier: BASF) and Genapol EC50 (Supplier Clariant).
  • the detergent product preferably comprises from 0.5 to 15 wt. % of nonionic surfactant.
  • the more preferred total amount of nonionic surfactants is from 2.0 to 8 wt. % and even more preferred is an amount of from 2.5 to 5.0 wt.%.
  • the nonionic surfactant used in the detergent product can be a single nonionic surfactant or a mixture of two or more non-ionic surfactants.
  • the nonionic surfactant is preferably present in amounts of 25 to 90 wt. % based on the total weight of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from 5 to 40 wt. % of the surfactant system.
  • Suitable anionic surfactants which may be used are preferably water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic surfactants are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the preferred anionic surfactants are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
  • the detergent product according to the invention comprises at least 5 wt. %, more preferably at least 8 wt. % and even more preferably at least 10 wt. % of bleaching agent by total weight of the product.
  • the bleaching agent preferably comprises a chlorine-, or bromine-releasing agent or a peroxygen compound.
  • the bleaching agent is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleaching agent is a peroxide. Most preferably, the bleaching agent is a percarbonate.
  • the detergent product of the invention may contain one or more bleach activators such as peroxyacid bleach precursors.
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N',N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4,751,015.
  • the detergent product comprises a bleach catalyst.
  • a bleach catalyst which is a manganese complex, such as Mn-Me TACN, as described in EP-A-0458397, and/or the sulphonimines of US-A- 5,041,232 and US-A-5,047,163. It is advantageous that the bleach catalyst is physically separated in the detergent product from the bleach (to avoid premature bleach activation). Cobalt or iron catalysts can also be used. Enzymes
  • the detergent product of the invention preferably comprises one or more enzymes chosen from proteases, alpha-amylases, cellulases, lipases, peroxidases/ oxidases, pectate lyases, and mannanases. Particularly preferred is protease, amylase or a combination thereof. If present the level of each enzyme is from 0.0001 to 1.0 wt.%, more preferably 0.001 to 0.8 wt. %.
  • Silicates are known detergent ingredients, and often included to provide dish wash care benefits, and reduce corrosion of dishware. Particularly preferred silicates are sodium disilicate, sodium metasilicate and crystalline phyllosilicates or mixtures thereof. If present the total amount of silicates preferably is from 1 to 15 wt. %, more preferably form 2 to 10 wt. % and even more preferably from 2.5 to 5.0 wt. % by weight of the detergent product. Perfume
  • the detergent product of the invention comprises one or more colorants, perfumes or a mixture thereof in an amount of from 0.0001 to 8 wt. %, more preferably from 0.001 to 4 wt. % and even more preferably from 0.001 to 1.5 wt. %.
  • Perfume is preferably present in the range from 0.1 to 1 wt. %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).
  • Preferred top- notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Shading dyes
  • shading dyes are for example added to laundry detergent formulations to enhance the whiteness of fabrics. Shading dyes are preferably blue or violet dyes which are substantive to fabric. A mixture of shading dyes may be used and indeed are preferred for treating mixed fiber textiles.
  • the preferred amount of shading dyes is from 0.00001 to 1.0 wt. %, preferably 0.0001 to 0.1 wt. % and particularly an amount of 0.001 to 0.01 wt. % is preferred.
  • Shading dyes are discussed in W02005/003274, W02006/032327, W02006/032397, W02006/045275, W02006/027086, W002008/017570, WO 2008/141880, W02009/132870,
  • the detergent product of the invention may be in any suitable form. Due to the presence of the solid of the invention it at least contains a solid part.
  • the remainder of the detergent product can also be non-solid, such as in the form of a liquid, but preferably contains at least one further non-powder non-liquid solid part, such as and preferably is a compacted powder (which is no longer considered a powder as such).
  • the detergent product is preferably provided as a water-soluble or water-dispersible unit dose.
  • Particularly preferred unit doses are in the form of pouches, which comprise at least one further non-shape stable ingredient, such as a liquid and/or powder; or in the form of tablets.
  • the unit dose is sized and shaped as to fit in the detergent cup of a conventional house-hold machine dishwasher, laundry machine or toilet-rim holder, as is known in the art.
  • the unit-dose detergent product has a unit weight of 5 to 50 grams, more preferably a unit weight of 10 to 30 grams, even more preferably a unit weight of 12 to 25 grams.
  • Advantageous unit dose pouches preferably have more than one compartment.
  • Advantageous unit dose tablets are those which have more than one visually distinct tablet region. Such regions can be formed by e.g. two distinct (colored) layers or a tablet having a main body and a distinct insert, such as forming a nested-egg.
  • multi-compartmental pouches/ multi-region tablets is that it can be used to reduce/prevent undesired chemical reactions between two or more ingredients during storage by physical segregation.
  • the more preferred unit dose is a tablet.
  • the unit dose detergent product is wrapped to improve hygiene and consumer safety.
  • the wrapper advantageously is based on water-soluble film which preferably a polyvinylalcohol (PVA) based film.
  • PVA polyvinylalcohol
  • Such wrapping prevents direct contact of the detergent product with the skin of the consumer when placing the unit dose in the detergent cup/holder of a e.g. machine dishwasher.
  • a further benefit of course is that the consumer also does not need to remove a water-soluble wrapping before use.
  • the detergent products according to the invention can be made using known methods and equipment in the field of detergent product manufacturing.
  • the detergent product according to the invention can be made by combining the solid of the invention together with the remainder of the detergent ingredients.
  • a particularly preferred way of combining is by pressing the solid onto (or into) the remainder of the tablet ingredients and/or by adding the solid in heated (liquid) form.
  • a highly preferred general detergent product formulation is as follows:
  • the product is preferably a unit-dose tablet with the following composition:
  • the product is preferably is a solid block composition, e.g. without comprising liquid parts and/or powder/granular parts and even more preferably having the following composition:
  • the process to manufacture the solid composition according of the invention has the benefit of being both simple, economical and omits the need for adding further crystal formation inhibitors.
  • Step I. of the process according to the invention is to provide an aqueous solution comprising: a) free acid equivalent of non-crystalline chiral aminopolycarboxylate; and b) free acid equivalent of non-crystalline organic acid different from a); and c) non-crystalline bismuth, non-crystalline zinc or a combination thereof, wherein the weight ratio of a):b) is from 1:2 to 8.8:1.
  • the combining of the ingredients at Step I. can be done in any order.
  • the amount of water to be used in providing the aqueous solution beneficially is sufficient to fully dissolve the ingredients a), b) and c) at boiling temperature to simplify processing.
  • Both the chiral aminopolycarboxylate and the organic acid may be added as a separate pre made aqueous solutions, which is preferred to further simplify processing.
  • Heat may be applied to (more quickly) dissolve the ingredients a), b) and c). Applying heat at Step I. is preferred as it not only reduces the time to dissolve (if necessary) the ingredients a) and b), but it may also reduce the amount of water needed to provide the solution, saving costs. Also having less water in the solution provided at Step I. can save time for completing Step II. of the process.
  • an aqueous solution is provided having a temperature of at least 50, more preferably of at least 70, even more preferably of at least 90, and still even more preferably of at least 100 degrees Celsius.
  • the aqueous solution at Step I. should be homogenous at least in respects of the chiral aminopolycarboxylate, the organic acid, the zinc and/or bismuth and the water. As such it is particularly preferred that the aqueous solution of Step I. is subjected to physical mixing.
  • the aqueous solution provided at Step I. may be viscous.
  • the aqueous solution provided at Step I comprises from 40 to 95 wt. % of water, preferably from 45 to 85 wt. %.
  • the final solid is preferably characterised by a highly preferred pH profile of at most 10.0, based on a solution of the solid in water in a 1:1 weight ratio, as measured at 25 degrees Celsius.
  • This can be easily achieved by suitably adjusting the pH of the aqueous solution accordingly, such as and preferably at Step I, using conventional means. For example, a balanced use of acid or (partially) neutralized salts forms of the ingredients a) and b) and c) can be applied.
  • Step II. of the process water is removed from the aqueous solution provided at Step I. by evaporation at a temperature of at least 50 degrees Celsius, to provide a water content of from 0.7 to 25 wt. %.
  • water is removed from the aqueous solution by evaporation at a temperature of at least 70 degrees Celsius, more preferably at least 90 degrees Celsius and most preferably at least 100 degrees Celsius.
  • the preferred way of removing water at Step II. is by applying sufficient heat to bring the aqueous solution provided at Step I. to a boil. This allows fast water removal which is advantageous to obtain the benefits of the solid according to the invention.
  • the water removal may be done by any suitable means but preferably is such that the water removal is on-par with boiling at otherwise standard ambient conditions, or faster.
  • Step II. does not involve spray-drying.
  • spray-drying can promote crystal formation and thus to reduce the translucency of the resulting solid.
  • spray-dried to a powder the powder requires further recombination into a substantial non-powder solid. This could be done e.g. by re-heating the powder, melting and cooling to form a solid of substantial size, but this requires substantially re working the product which is time and energy intensive.
  • Step III. the temperature is of the desiccated mixture is preferably reduced to less than 45°C to obtain a solid. More preferably the temperature is reduced to less than 40, 35, 30 degrees Celsius even more preferably to from 15 to 25 degrees Celsius and still even more preferably to from 20 to 25 degrees Celsius to obtain a solid.
  • Step III. can be performed use passive or active cooling. Active cooling may be done using any conventional means such as by refrigeration.
  • the cooling of the desiccated mixture is achieved by heat exchange with the remainder of the (cooler) detergent product parts.
  • the ‘solid’ is applied in liquid/viscous form having an elevated temperature, onto the remainder of the detergent product and allowed to solidify in situ.
  • the solid according to the invention is obtainable by the process according to the invention. Solids made according to the process of the invention were shown to be highly beneficial in view of the previously indicated attributes.
  • XRD is used to detect presence of crystalline material in the solid using to the Wide- Angle X-ray Scattering technique (WAXS).
  • WAXS Wide- Angle X-ray Scattering technique
  • XRD is carried out using a D8 Discover X- Ray Diffractometer from Bruker AXS (activa number: 114175). The XRD measurements is performed using the following settings:
  • DSC Differential Scanning Calorimetry
  • Tg glass transition temperature of the solid.
  • the equipment used of the DSC analysis was a Perkin Elmer power compensated DSC8000 equipped with an Intracooler III as cooling means.
  • the stainless-steel sample pan is used which is provided with the equipment by the Supplier and filled according to Supplier instructions with material to be analyzed.
  • the amount of material added to the sample pan is from 10 to 40 mg. The following settings are to be used in running the measurement:
  • the Tg of the samples is measured with the second heating (i.e. the last heating step in the DSC temperature regime). Gloss measurement
  • UV Filer Pos/UV Energy UVD65/Cal/UVCal. • and calibrated according to Supplier instructions before measurement.
  • Example 1 Solid compositions according to the invention (Example 1 and Example 2) and not according to the invention (Comparative A) were made starting from an aqueous solution having a composition as set out in the following Table A.
  • Table A Composition of aqueous solutions. The amounts are given in wt. % parts. 1
  • GLDA Dissolvine GL-47-S (Supplier: Akzo Nobel) is a 47 % solution of GLDA containing 50 % water. The amount given in Table A is the amount of GLDA.
  • Citric Acid used as a 50 % solution.
  • the amount given in Table A is the amount citric acid.
  • Polyacrylate Sokalan PA 25 CL (Supplier BASF), supplied as granules comprising 80% polyacrylate. Average molar mass Mw is 4000. The amount in Table A is the amount of polyacrylate.
  • Example 1 The aqueous solutions were heated to boiling in a jacketed vessel. Next, the pourable material was poured onto a plate and allowed to cool and solidify. The solid compositions according were subsequently analyzed. First, the translucency was evaluated by eye. All the compositions were transparent, glossy and thermoplastic. The solid composition of Example 1 had a metallic grey sheen and was found to have a marked increase in glossiness compared to Example 1 and Comparative A.

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Abstract

L'invention concerne une composition solide comprenant : a) de 25 à 88 % en poids d'équivalent acide libre d'aminopolycarboxylate chiral non cristallin ; et b) de 10 à 60 % en poids d'équivalent acide libre d'acide organique non cristallin différent de l'aminopolycarboxylate ; et c) de 0,0005 à 4 % en poids de bismuth non cristallin, de zinc non cristallin ou d'une combinaison de ceux-ci ; et d) de 0,7 à 25 % en poids d'eau ; l'acide organique ayant une masse moléculaire moyenne d'au plus 500 Daltons, la masse moléculaire étant basée sur l'équivalent acide libre.
PCT/EP2020/073326 2019-08-21 2020-08-20 Composition solide de détergent WO2021032834A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20758223.0A EP4017957B1 (fr) 2019-08-21 2020-08-20 Composition détergente solide
CN202080058501.9A CN114286854A (zh) 2019-08-21 2020-08-20 洗涤剂固体组合物
ES20758223T ES2944450T3 (es) 2019-08-21 2020-08-20 Composición sólida detergente

Applications Claiming Priority (12)

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EP19192828.2 2019-08-21
EP19192827.4 2019-08-21
EP19192831 2019-08-21
EP19192831.6 2019-08-21
EP19192836 2019-08-21
EP19192828 2019-08-21
EP19192833.2 2019-08-21
EP19192834 2019-08-21
EP19192827 2019-08-21
EP19192833 2019-08-21
EP19192836.5 2019-08-21
EP19192834.0 2019-08-21

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PCT/EP2020/073279 WO2021032816A1 (fr) 2019-08-21 2020-08-20 Composition solide détergente
PCT/EP2020/073278 WO2021032815A1 (fr) 2019-08-21 2020-08-20 Solide détergent gaufré
PCT/EP2020/073326 WO2021032834A1 (fr) 2019-08-21 2020-08-20 Composition solide de détergent
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PCT/EP2020/073279 WO2021032816A1 (fr) 2019-08-21 2020-08-20 Composition solide détergente
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ES2945459T3 (es) 2023-07-03
CN114269889A (zh) 2022-04-01
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WO2021032815A1 (fr) 2021-02-25
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